Treatment of cellulosic yarns by rubbery materials, and textiles thereof



United States Patent TREATM NT OF CELLULOSIC YARNS BY RUB- BERYMATERIALS, AND TEXTILES THEREOF Edward Abrams, Birmingham, Ala., andNeil H. Sherwood, Avon Lake, Ohio, assignors to The B. F. GoodrichCompany, New York, N. Y., a corporation of New York No Drawing.Application March 1, 1954 Serial No. 413,420

18 Claims. (Cl. 8-18) The present invention relates to the treatment oftextiles with polymeric materials. More particularly, it relates to amethod for treating cellulose-containing materials, especially cotton,in the form of yarn with a copolymer containing a butadiene hydrocarbonand an acrylic nitrile and to the product of suchmethod.

It is conventional practice to apply starch as a size material tocellulose-containing textile yarns prior to weaving them into cloth. Thestarch reduces the shedding of the yarn as it is woven, that is, itreduces'the loss of fine fibers or filaments of the yarn as it travelsthrough the weaving machinery as well as increasing the abrasionresistance of the yarn. The starch also gives some stiffness to thewoven fabric so that it can readily be cut into the desired pieces andshapes when being manufactured into garments. However, starch is not apermanent size, and on washing it is very rapidly lost from the cloth tomaterially reduce its abrasion resistance and consequently its life andusefulness. Moreover, during washing the dyes used are removed so thatthe color fades or bleeds or crocking occurs. Furthermore, in new,unlaundered fabrics a drop of water or other starch solubilizing liquidwill cause spotting of the cloth due to loss of starch or'itsredistribution at that point, necessitating extreme care inmanufacturing and handling operations to avoid the production ofunsightly, second grade material. T 0 remove the starch from thefinished fabric and to treat the fabric with fabric-strengtheningmaterials requires several subsequent treating steps which addmaterially to the cost of finished goods so that such methods areuneconomical and impracticable. On the other hand, leaving the starch inthe fabric and applying a fabric-strengthening coating is alsoundesirable since permanent abrasion resistance is not materiallyimproved.

The difficulties alluded to above are particularly troublesome whenusing blue denim yarn to make fabric. Blue denim is normally made fromrelatively short staple cotton averaging inch in length and is dyed withindigo which is actually a pigment rather than a dye. The blue pigmentis on the surface of the yarn and is rather easily removed by abrasion.Moreover, the abrasion resistance of blue denim fabric is rather poor.However, there are no known methods of improving the yarn and fabricwithout very substantially increasing the cost of the fabric so that itis noncompetitive. I Accordingly, it is a primary. object of the presentinvention to provide cellulose-containing textiles' witha' dyed orundy'fed cellulose-containing yarns with a per 2 manent sizematerialwhich produces a yarn having low shed value and high abrasionresistance.

It is still another object of the present invention to provide dyed orundyed cellulose-containing fabrics from yarns having a permanent sizethereon, said fabrics characterized by exhibiting an abrasion resistanceafter repeated laundering substantially superior to the abrasionresistance of a similarly laundered fabric made from starch-sized warpyarns.

A further object of this invention is to provide a method for treatingcellulose-containing yarns with a permanent size.

Yet another object of this invention is to provide a method for applyinga permanent size material to cellulose-containing yarn which may then bewoven into cloth, said yarn and said cloth being dyedor undyed.

Still another object is to provide a method for simultaneously dyeingand permanently sizing cellulose-containing yarn and weaving said yarninto cloth which exhibits high abrasion resistance after repeatedlaundering with little or no loss of color.

These and other objects and advantages of the present invention willbecome more apparent to those skilled in the art from the followingdetailed description, examples and tables. 7 V g g It now has been foundaccording to the present invention that cellulose-containing textileyarns can readily be provided with a permanent size by treatment with anaqueous dispersion or latex of a copolymer of a butadiene hydrocarbonand an acrylic nitrile to provide a minor amount of a discontinuouscoating of the copolymer on the yarn. The copolymer affords low shed.value and high abrasion resistance. Yarns treated accord ing to thepresent invention can be readily woven into cloth which exhibitsexcellent hand. After repeated launderings, the yarn as well as thecloth retain a substantial degree of their original abrasion resistanceand show little if any bleeding of dyes or pigments contained therein. v

The. copolymer employed in the sizing bath is a copolymer containing abutadiene hydrocarbon and an acrylic nitrile. Examples of butadienehydrocarbon monomers copolymerizable with the acrylic nitrile monomerare those open-chain conjugated dienes having from 4 to 8,carbon atomssuch as butadiene-1,3, isoprene, 1,3- pentadiene, methyl pentadiene andthe like and mixtures thereof, butadiene-1,3 being preferred. One ormore acrylic nitrile monomers copolymerizable with the butadienehydrocarbon monomers are acrylonitrile itself,

methyl acrylonitrile, ethyl acrylonitrile, and chlorocan contain atleast one other monomer copolymerizable therewith such as styrene,chlorostyrene, methacrylic acid, methyl acrylate, methyl methacrylate,ethyl acrylate,

ethyl methacrylate, 2-vinyl pyridine,methyl, vinyl ketone, andvinylidene chloride in amounts up to 35% by weight,

The copolymer is employed generally in neutral or alkaline latex for-malthough acid latex may be used. It can be used as a dispersion of from3 to 55% total copolymer solids having an average particle size of fromabout,.02 to .20 micron, preferably about .06 micron. However, for easeof application and mixing with other components, the latex is employedpreferably in dispersions containing from about 6 to 20% by weight ofcopolymer solids. It will be understood that a high solids latexmay bediluted with the water present in conjunction with the other elements ofthe textile size treating bathto provide the desired solids content inthe dis persion and conversely a dilute latex may be brought to thedesired solidscontent when less water is employed with the otherconstituents. Moreover, considerable variation can be made in copolymersolids content depending on typesof yarn, running speeds, temperatures,particle size of the copolymer, slashing equipment and the like. Forexample, sizing baths. of dispersions of about 1% solids will depositabout.2% solids; Still other dispersion's containing 30% solids can beused to deposit 36% solids on the yarn. Further, a dispersion of 20%solids can deposit 8% solids on the yarn where another dispersionof-about solids will deposit 4% or 7%. On a dry weight basis the amountof copolymer employed in the treating bath varies as is necessary toachieve 'a yarn pickup of about 2 to and preferably fromabout 4 to 14%by weight. The best results are obtainedwith a pickup of 6-8% ontheyarn. Outside of these ranges insufficient copolymer will be present onthe yarn toeffectively size *or too much will be present found desirableas well as bactencides, flame-proofing,

agents, fungicides,*water repellent materials and the like. Starch maybe :added to stiffen the fabric and reduce pilling.

The textiles to be treated according to the present invention' 'arepredominantly cellulose materials such as cotton, viscose rayon,cellulose "acetate, regenerated cellulose'and mixtures thereof as wellasblends of cellulose materials with other textile materials such as wool,nylon and the like'wherein the cellulose material is present in atleastamajoramount. While the present invention will be'described withparticular reference to the treatment of warp yarns to be used inweaving fabrics such as square woven fabrics,twills,fancies and thelike, it is to be understood that the filling or weft yarns may besimilarly treated and likewise, knitted goods and other textile fabricswhere a permanent 'sizeis desired.

Dyesnorspigrnents can be incorporated into theyarn prior to treatmentwith the latex dispersion. Alternatively, the latex treated yarns can bedried and then treated with dyes or pigments, or woven into fabricwhichis then dyed or pigmented. Moreover, dyes or pigments canbe-incorporated into the bath so that yarn sizing and dyeing areaccomplishedsimultaneously. Thedy'es or pigments employed maybe thosewhich will color thetextile or the latex or both with the same or.different colors. Cross-dyeing can also be employed. In some instances,the latex deposited on the yarncan be dyed to. provide afabric which hasthe overall appearance of being completelydye'd although microscopicexamination will' 'show that only the latex particles on the yarn willactually have beensusceptibleto thedye V 1 In sizing yarns according tothemethod of thepresent inventiomjthe yarns, preferably warpyarns, aredelivered from beams to the latex size bath and carried over rollers ata speed suflicientto deposit a minor amount of latex on the outersurface layers of the yarns which are than passed through squeeze rollsto remove the excess latex from the yarns and to cause some impregnationin the outer fiber layers of the yarn. Variations in dipping times willmake some change in latex solids on the yarn. However, such do notadversely affect results. For example the bath can be operated at yarnrunning speeds of from 5 to 10 yards per minute to provide a solidspick-up of from 5.6 to 5.7% with Walker Abrader abrasion cycles of64-63. If the squeeze rolls become coated with copolymer and tend tocause sticking, they can be coated with silicone grease or. similarmaterial which prevents buildup of copolymer or a material such aspolyethylene glycol in a minor amount maybe added to the size bath,particularly where the yarns themselves tend to exhibit some sticking.The latex treated yarns are next dried in an oven or on dry cans for asuflicient period of time to coagulate and set the latex and reduce thetotal moisture content to not more than about 5% by weight. Drying ofHycar sized yarns to a moisture content of not more than 5% eliminatesessentially all of the tacky and rubbery feeling the sized yarn mightexhibit and removes the water of dispersion from the deposited latex.The substantially dried yarns may then be woven into cloth with unsizedfilling yarns. If desired, the filling yarns can be coated with latexsize prior to weaving.

Moreover, the size bath containing the butadiene-nitrile aqueousdispersion of the present invention can be operated at temperatures offrom to F. to obtain solidson the yarn averaging from 5.7 to 4.2% byweight of the yarn with Walker Abrader abrasion cycles of 64-70. On theother hand, starch must be made up in special equipment at the boil andmust be applied to the yarn hot or at the boil. If it is not used up ina short time, it is subject to mold growth whereas thebutadieneacrylonitrile copolymer latex is essentially unaffected.Moreover, additives are required in many instances to give the starchsatisfactory sizing characteristics.

Yarns prepared according to the present invention have a discontinuousthin adherent coating of copolymer thereon rather than a thickimpervious continuous coating. Under a microscope. the copolymer appearsto be distributed as particles over the body of the yarn and may appearto be in the form of a fine network. This arrangement of the copolymeron the yarn and outer fiber layers is advantageous as'it permits theyarn to flex without ravelling or shedding during weaving and alsopermits dyes or pigments to readily penetrate the fibers if it isdesired to dye the yarns after latex sizing. The shedding and abrasionresistance of the latex sized yarns is as good as starch sized yarns,and, after repeated launderings, latex sized yarns have up to twice theabrasion resistance of conventional starch sized yarns and do notappreciably bleed as compared'to starchsized yarns.

The presence of the discontinuous copolymer on the surface of the yarnand in its outer fiber layers as well as in cloth manufactured from suchyarn lends itself readily to subsequent compressive shrinkage treatmentsso that the yarn or fabric may be preshrunk if desired according toknown processes without any adverse effects, prior to manufacturing intogarments. It, also, is a feature of cloth prepared from the latex sizedyarns of the present invention that the latex although in a discontinuous coating on the yarn contacts the filling yarns so that in thearea of contact between the warp and filling yarns there is anappreciable amount of copolymer present to prevent abrasion as the yarnsflex. This is a contrast to conventional coating processes where onlythe exposed areas of the yarns not in contact with each other are coatedwith a thick layer. The importance of using the-copolymer of a butadienehydrocarbon and an acrylic nitrile as a permanent size for yarn Q isthat it o fiers equal or :better shed value and abrasion resistance ascompared to starch and increased abrasion resistance to the finishedcloth and eliminates the necessity for removing the starch and applyingsubsequent coatings of copolymer after the fabric is woven. Thus,applying the copolymer to the yarn itself eliminates many subsequenttreatment steps. Also, fabrics woven from yarns sized as disclosedherein have a hand which is satisfactory for subsequent manufacturingoperations.

The following examples will serve to illustrate the invention with moreparticularity to those skilled in the art.

EXAMPLE I A size bath containing a latex dispersion of a 55-45 copolymerof butadiene-1,3 and acrylonitrile (total solids about 6.0% and having aparticle size of about 0.06 micron) was prepared in a stainless steelsize box of a slasher. Unsized blue denim cotton yarns (8.75s containingabout 11% indigo) on 4' beams each containing 42 ends was fed as'a sheetof 168 ends lying sideby-side into the bath at room temperature overrollers and between two rubber coated squeeze rolls into a drying ovenat 300 F. and at a rate sufiicient to afford a moisture content of about5% by weight after drying. The dried and sized yarns were separated fromeach other by means of split bars and then collected on a spool. Thepercent by weight of copolymer on the yarn was 4.08%.

A portion of the latex treated yarn was tested ona Southern ResearchInstitute Shed Tester which is essentially a miniature loom without thefilling motion. It is equipped with a double set of harnesses, a reed,and dropwires for automatic stop motion when yarns break. In operationthe reed is caused to strike an impact bar simulating the action of thereed on a standard loom. About yards of sized (one yard of unsized) warpyarns are passed through the shed tester in each test during the spaceof about four hours. The fibers and size that are abraded from the yarndrop to the bottom and are collected in an enclosed pan. This material,called shed, is weighed and the result is expressed as percent of theweight of the total yarn tested. Results of shed tests are reproducibleto less than 0.1%. When using the above butadiene-acrylonitrile latex, ashed value of 1.57% was obtained. With 8.6% by weight starch as a sizeon the yarn, the shed value Was 1.30% and the control (unsized) showed ashed value of 3.27%. The breaking strengths in pounds of the three typesof yarns using ten inch lengths were: latex sized-3.36, starch sized3.34and unsized-3.13

Another portion of the above latex treated yarn was tested on a WalkerAbrader which is manufactured by the U. S. Testing Company, Hoboken, NewJersey. This machine causes yarns to rub against each other until thereis a break. The number of abrading cycles which is required to cause abreak is recorded. In practice, 24 strands of a given sample of yarn aremounted on the machine. As each yarn breaks, the machine stops and thenumber of cycles is read from a counter. After 12 consecutive breaks arerecorded, the machine is stopped and the remaining 12 strands arediscarded. Four sets of abrasion data are obtained for each yarn sample.The average value is the grand average of all 48 determinations for eachyarn sample. Average Walker Abrader cycles for the latex treated yarnwere 67 while for the starch sized and unsized yarn it was 38 and 18,respectively.

All shed and abrasion resistance tests were made in a conditioned roomcontrolled at 70 F. and 65% R. H. The above example shows that shedvalues for latex treated yarns are nearly equal to those for starchsized yarns even when the amount of latex is half that of starch whereasthe abrasion resistance of the latex sized yarn was 76% greater than thestarch sized yarns.

Blue denim yarns were also sized in a commercial plant slasher but in amanner similar to that in the above example, and then were wovenintofabric, washed in a Launderometer and tested on a Taber Abraser. Theresults of these tests are shown in Table A below:

Table A I ABRASION RESISTANCE or FABRIC CONTAINING Bum-DIENE-1,3/ACRYLONITRILE TREATED WARP YARNS Peacent Launderometer cycles3 Run Fabric weight No. designalatex 0 1 2 3 4 5 tlon solids on warpyarns Taber abraser wear cycles 1 D 2 10 1, 501 1, 372 1,078 944 905 889D 8 l, 312 1, 404 1, 498 1, 591 1, 654 1, 791 D 9. 8 1, 306 1, 388 1,453 1, 547 1, 623 1, 809 4 SD 2 10 831 722 685 597 554 538 5 SD 7. 4 657783 913 1,019 1,094 1, 167 6 SD 7. 1 590 630 807 952 1, 047 1, 129 7 WE2 10 1, 775 1, 284 1, 273 1, 345 1, 276 1, 151 8. WB 9. 2 l, 855 1, 9452, 049 2, 123 2, 292 2, 407

=GS-10 new calibrase wheels. =Starch. D=8 oz. blue denim. V SDLightweight sport denim. WB=11 oz. white back denim.

The above results show that while in some cases the unlaundered fabricin which the warp yarns were sized with latex did not show as highvalues as the starch sized fabric, the abrasion cycles increased for thelatex sized fabrics after repeated launderings whereas the abrasioncycles decreased for the starch sized fabrics. Remarkably, at the end of5 washings the latex sized yarns are twice as abrasion resistant as thestarch sized yarns even when using less latex solids on the yarn thanstarch.

solids. Moreovenafter 5 launderings the fabrics having latex sized yarnsincreased in abrasion resistance as much as from 30 to of their abrasionresistance before laundering and exhibited greater abrasion resistancesthan similar unlaundered fabrics of starch sized yarns. Furthermore,when samples of starch sized fabric werelaundered and ironed with whitecloth after each cycle they colored the wash water and the white clothblue whereas the latex sized sample did not appreciably color the washwater and showed only a slight color transfer after the first launderingbut no appreciable transfer of color to the white cloth thereafter. It,thus, is seen that in addition toimproved abrasion resistance, the latexreduces bleeding or leaching dun'ng washing and color transfer orcrocking during laundering and ironing.

EXAMPLE H Blue denim yarns were also treated in the manner described inExample I, above, except that a size bath containing 6% solids ofvarious mixtures of starch and 55-45 butadiene-l,3-acrylonitrilecopolymer were used. Tests on these yarns gave the following data:

' Table B PROPERTIES OF YARNS HAVING MIXED COATINGS tained. However,after the second laundering, no color was in the wash water which showedthat the copolymer prevented bleeding. Further, while heat is requiredto bring the starch into the colloidal or dispersed state, no additionalheat is required after addition of the copolymer dispersion so that thesize bath may operate at room temperature. The bath also is not subjectto spoilage for extended periods of time. Accordingly, such mixtureswill be useful'where a very high abrasion resistance is not required.

EXAMPLE III Further tests were conducted on yarns and fabrics from theseyarns prepared as described in Example 1 supra but in which the pressureon the squeeze rolls and the type of rolls used in the treatment wasvaried. The results of the tests are indicated in Table C below:

. Table C VARIATIONS. IN METHOD OF APPLYING OOPOLYMER SIZE I Total YarnFabric (8.75s) latex solids Taber abraser Run in size Total cy'cles,avg. No. bath, latex Walker 7 Slasher conditions percent solids, abradcrby percent cycles, As re- After 5 weight by avg. ceived launwelghtderings 1. 0 18 Impossible to weave unsized yarn 2..- p i 12 p 1 10 52432 245 1 rubber roll, 1 wool roll, medium prest i sure. 3. 6 2.8 40438' 521 2 rubber rolls, medium pressure. 4 10 3. 3 30 343 348 Do. 16 3.3 35 361 494 Do. 20 6. (i 46. 445 544 1 rubber roll, 1 yarn wound roll,medium pressure. 7 20 7. 3 48 332 504 1 rubber roll, 1 yarn wound roll,high pressure. 8L; 20 11.6 54 321 499 1 rubber roll, 1 yarn wound roll,high pressure, Santomerse in size bath.

- ==averagc of 48 determinatlons.

:= callbrase wheels-average ol 5 determinations. c

These testsshow that the squeeze rolls and the pressure'thereon canbevaried with achievement of comparable results. 1 As was shown in TableA, the latex' sized material in Table C also increased in abrasionresistance after laundering as compared to the starch sized material.However, in one instance (test 4 Table C) after 5 launderings the latex.sized material wasnot asabrasion resistant. as the unwashed starch sizedmate Yarns were also sized according to the method of.Ex-. ample I.supra exceptthat the amount of latex. solidsin the size bath was varied.The amount of latex solids on the resulting sized yarn and-the abrasionresistance and shed values of the various sized yarns are shown inTable.

D below:

Table D RESULTS OF VARY-INC LATEX CONTENT OF SIZE BATH AND OF YARNPercent Percent Walker Percent Run No. by weight by weight abraderhy'weight latex solids latex solids cycles, shed in bath on yarn avg. V

0 0 18 3. 27 12 l 8.6 38 1. 30 0. 4 1. 8 34 3. 22 1. 2 2. 0 43 2. 75 2.02. 2 48 2.30 3.9 2. 5 62 1. 5. 9 4. 2' 68' 1.39 6.0 1 6. 6 I61 1. 30 7.0 6. 1 61 1. 22 9.8 7.0 58 1. 21 14; 0 12. 5 57 1. 40 4 15 18. 0 1081.50 i 20 8 6l 1. 20

1 Starch {Plus 10 PER-of curing agent.

Afterpne laundering 97; after five launderings-l30. Plus minor amountpolyethylene glycol.

I After one laundering-56; alter live launderings57. Plant date.

. with respect to ExampleVI. 65'

, color fastness test No. 2.

8 The above table indicates that the amount of latex in the sizebath andon the yarn can be varied considerably with obtainment of satisfactoryresults. The best combination of shed value and abrasion resistance liesin the range of from about 4-t0 14.0% by weight of copolymer on theyarn. This range of copolymer can be achieved from bathshaving variousconcentrations of copolymer which will deposit varying amounts ofcopolymer on the yarn. Acceptable coatings can still be obtained wherethe bath will deposit as little as 2% and as much as 20% copolymer onthe yarn.

7 EXAMPLE V Still other yarns were sized according to the method of theExample 1, above, in which the particle size of thebutadiene-l,3-acrylonitrile copolymer in the latex was varied as well asthe ratio of'diene to nitrile. in Table E below, considerable variationcan be realized withobtainment of satisfactory results.

- Table E EFFECT OF- COPOLYMER- PARTICLE SIZE Ratio Average PercentWalker Break- Run diene to particle pickup Shed, abrader ing N o nltrilel size, on percent cycles, strength,

micron. yarn avg. lb.

1 Charging ratio; resulting polymer ratios are similar. 1 Plus about2.86 parts methacrylic acid.

EXAMPLE VI Cotton yarns whichhad not been dyed or sized were passedthrough a" 67-3 3 butadiene-1,3-acrylonitrile sizeto employsomewhat'less dye in the bath; Swatches from each of. the dycingswere.tested in the Launderometer, No fading or discoloration occurredwitlithe, vat dyed samples. There was slight fading and transfer ofcolor in the direct dyed samples, although the copolymer sized sampleexhibited less discoloration than the control. Cotton cloth woven withcopolymer sized. warp yarn and subsequently dyed exhibited similarresults.

EXAMPLE VII Cotton yarns were treated in the same manner as Example VI,above, exceptthat the size bath contained 30%' totalsolids and thepickup on the yarns was about 36%; Samples of yarns were dyed in thesame manner as shown in-ExampleVI and'compared with controls. Theresults obtained were the same as disclosed above Cotton cloth wovenwith copolymer sized warp yarn and subsequently dyed exhibited similarresults.

Examples VI and VII demonstrate that copolymer sized yarns can bereadily dyed with either vat dyes or direct dyes. Further, high solidscontent of copolymer on the yarn doesnot adversely affect-the action ofthe dyes. While a large amount of copolymer on the yarn is not generallynecessary to afford a yarn having the desired abrasion resistance andshed value, such can be used if desired-and'will notpreventpickup of dyeby the yarn. These'results would also indicate that-the copolymer is Asshown' not depositedas a continuous impervious coating on the yarns butrather as a discontinuous, pervious coating.

EXAMPLE VIII weight'of the bath of oxidized indigo. After heating for. afew minutes the yarns were withdrawn, dried, and

placed in an alkaline bath containing sodium hydrosulfite to reduce theindigo. permitted to air oxidize. They exhibited the conventional bluecolor of indigo and contained about 6% copolymer solids. I

In addition to showing the utility of butadiene-acrylonitrile copolymersized yarn during dyeing, Example VIII is of special significance whenconsideration is given to conventional indigo dyeing and starch sizingof denim.

In practice the yarn is dipped in reduced indigo dye vats of increasingconcentration'in a seriesof six steps followed by oxidation after eachstep, drying and then finally butadiene-l,3 and acrylonitrile (15% totalsolids).

The bath was slightly acid and contained additionally about 3% by weightof an acetatedye (Eastman Eastone Fast Red GLF). After 45 minutesat 180F., .the yarns were removed from the bath and washed. ,They were coloredred and contained about :6% copolymer solids. Microscopic examination ofthe yarn revealed that the copolymer was distributed over the yarn asfine globules and each particle of the copolymer, was dyed rather thanthe fibers of the yarn.

In summary, the present invention teaches that cellulose-containing yarncan readily be treated with a dispersion or latex copolymer of abutadiene hydrocarbon and an acrylic nitrile and'woven'into cloth toprovide a permanent size. The yarn-has a low shed value and highabrasion resistance. Even on repeated launderings the fabric containingthe polymer size does not appreciably decrease in abrasion resistance.Moreover, little if any bleeding or crocking the the dyes or pigmentsoccurs when yarn is treated as disclosed herein. The yarns so treatedcan be dyed and then readily woven into cloth which is unexpected inview of the nature of the copolymer. Alternatively, the dyeing step canfollow Weaving of the yarn into cloth or dyeing can occur simultaneouslywith sizing. Furthermore, permanent high abrasion resistance is impartedto the cloth. This process obviates the conventional starch sizing andsubsequent desizing and coating steps. The present invention, hence,provides a novel way of treating yarn so that it can be woven intocloth, with permanent retention of the properties provided to the cloth.Furthermore, cloth prepared from yarn as treatedherein has an excellenthand suitable for cutting and finishing operations and can be readilypre-shrunk by compressive methods.

We claim:

1. The method of treating predominantly cellulose containing yarn toimprove its abrasion resistance, to improve its resistance to crockingand bleeding when dyed and to reduce its shed loss which comprisesapplying to said yarn an aqueous dispersion containing from 3 to 55% byWeight of solids of a rubbery material selected from the groupconsisting of a polymer of a diene monomer and a nitrile monomer and apolymer of a diene monomer and a nitrile monomer with up to 35% byweight of said second named polymer of a copolymerized monomer selectedfrom the group consisting of styrene,

The yarns were then removed and ill) chlorostyrene, methacrylic acid,methyl acrylate'methyl methacrylate, ethyl acrylate, ethyl methacrylate,2-vinyl pyridine, methyl vinyl ketone and vinylidene chloride, saiddiene being an open chain conjugated diene hydrocarbon having from 4 to8 carbon atoms and being present in said polymers in an amount of from35 to by weight and said nitrile being selected from the groupconsisting of acrylonitrile, methyl acrylonitrile, ethyl acrylonitrile.and ehloroacrylonitrile and mixtures thereof,

to deposit from above 2 to 20% by weight of said solids on said yarn anddrying said yarn containing said solids to a total moisture content ofnot more than about 5% by weight, to'coagulate, set and obtain adiscontinuous coating of said rubbery material on said yarn.

2. The method of treating predominantly cellulose containing yarn toimprove its abrasion resistance, to improve its resistance to crockingand bleedingv when dyed and to reduce its shed loss'which comprisesapplying to said yarn an aqueous dispersion containing from about 6 to20% by Weight of solids of a rubbery material selected from the groupconsisting of a polymer of a diene monomer and a nitrile monomer and apolymer of a diene monomer and a nitrile monomer with up to 35% byweight of said second named polymer of a copolymerized monomer selectedfrom the group consisting of styrene, ehlorostyrene, methacrylic acid,methyl acrylate, methyl methacrylate, ethyl acrylate, ethylmethacrylate, 2-vinyl pyridine, methyl vinyl ketone and vinylidenechloride, said diene being an. open chainconjugateddiene hydrocarbonhaving from 4 to. 8 carbon atoms and being present in said polymers inan amount of from about 55 to 70% by Weight, and said nitrile" beingselected from the group consisting of acrylonitrile,;

reduce its'shed loss which comprises: applying to said.

yarn anaqueousdispersion containing from'about 6 to 20% by weight ofsolids of a rubbery material selected from the group consisting of apolymer of a diene monomer and a nitrile monomer and a polymer of adiene monomer and a nitrilemonomer with up to 35% by weight of saidsecond named polymer of a copolymeriz'ed mono-- mer selected from thegroup consisting of styrene, chloros'tyrene, methacrylic acid, methylacrylate, methyl methacrylate, ethyl: acrylate, ethyl methacrylate,2-vinyl pyri dine, methyl vinyl ketone and vinylidene chloride, saiddiene being an'open chain conjugated diene hydrocarbon having from 4 to.8 carbon atoms and being present in said polymers in an amount of fromabout 55 'to 70% by weight, said nitrile being selected from the groupconsisting of acrylonitrile, methyl acrylonitrile, ethyl acrylonitrileand chloroacrylonitrile and mixtures thereof, and said solids having anaverage particle size of from about .02 to .20 micron, to deposit fromabout 6 to 8% by weight of said solids on the yarn and drying said yarncontaining said solids to a moisture content of not more than about 5%by weight, to coagulate, set and obtain a discontinuous coating of saidrubbery material on said yarn.

4. The method according to claim 3 containing the additional step ofweaving said coated yarn into a fabric.

5. The method according to claim 4 containing the additional step ofdyeing said fabric.

6. The method according to claim 3 containing the additional step ofdyeing said yarn prior to applying said dispersion thereto.

7. The method according, to claim 3 containingthe 1.1 additional stepof.dyeing said yarn after'said dispersion has been applied thereto.

8. The method according to claim. 3 in which said dispersionadditionally contains a dye.

9.The. method according to claim 8 in which said dye is an oxidized vatdye, said rubbery material is a co-.

polymer of butadiene-l,3 and acrylonitrile,. said; solids. havean'average particle size of about .06micron and said yarn is cotton and.containing the additional steps. of.

containing yarn having from above 2 to 20% by weight.

on said yarn of a coagulated, set and discontinuous coating of a rubberymaterial selected from the group consisting of. a polymer of a dienemonomer and a nitrile monomer and aipolymer of .a diene monomer and anitrile monomer with up to by weight of said second named polymer of acopolymerized monomer selected from the group consisting of styrene,chlorostyrene, methacrylic acid, methyl acrylate, methyl methacrylate,ethyl acrylate, ethyl methacrylate,.Z-vinyl pyridine, methyl vinylketone and vinylidene chloride, said diene being an. open chainconjugated diene hydrocarbon having from 4 to 8 carbon atoms and beingpresent in said polymers in an amount of from 35 to 90% by. weight andsaid nitrile being 'selectedtfrom the group consisting .of.acrylonitrile, methyl acrylonitrile,

ethylacrylonitrile and chloroacrylonitrile and: mixtures thereofpsaidcoated yarn exhibiting improved abrasion resistance, improved resistanceto crocking and bleeding whendyed and a reduction in shed lossand being.essentially dry and non-tacky.

12'. Textile material having predominantly cellulose containingyarnhaving from about 4 to 14% by weight on said yarn of a coagulated, setand discontinuous coating of a rubbery material selected from'the group.con-: sisting of a polymer of a diene monomer and a nitrile monomeranda polymer ofa dienemonomer and a nitrile monomerwith up to 35% byweight of said secondsnamed polymer ofa copolymerized monomer selectedfrom the group consisting of styrene, chlorostyrene, methacrylic' acid,methyl acrylate, methyl methacrylate,.ethyl acrylate,. ethylmethacrylate, 2-vinyl pyridine, .methyl vinyl. ketone? and. vinylidenechloride, said diene'being: an openchain conjugated diene hydrocarbonhaving from '4 to 8 carbon atoms and being present in said polymersin-an amount'of' abrasion resistance, .improved resistance to crockingand bleeding when dyed and a reduction in shed essentially dry andnon-tacky.

13. Textile material having predominantly cellulose containing yarnhaving from about 6 to 8% by weight on said yarn of a coagulated, setand discontinuous coatloss and being' mer and a polymer of a dienemonomer and a nitrile monomer with up to 35% by weight of said secondnamed polymer of a monomer selected from the group consisting ofstyrene, chlorostyrene, methacrylic acid, methyl acry-' late, methylmethacrylate, ethyl acrylate, ethy-l methacry l'ate, Z-viriyl pyridine,methyl vinyl ketone and vinylidene chloiide,;said diene being an openchain conjugated diene hydrocarbon having from 4 to 8 carbon atoms andbeing present in said polymers in an amount of from about 55 to byweight and said nitrile being selected from the group consisting ofacrylonitrile, methyl acrylonitrile, ethyl acrylonitrile andchloroacrylonitrile and mixtures thereof, said coated yarn exhibitingimproved abrasion resistance, improved resistance to crocking andbleeding when dyed and a reduction in shed loss and being essentiallydry and non-tacky.

1-4. Textile material according to claim 13 containing additionally adye.

1'5. Textile material according to claim 14 in which said dye is a vatdye, said rubbery material is a copolymer of butadiene-1,3 andacrylonitrile and said yarn is cotton.

16. Textile material according to claim 14 inwhich said dye is indigo. aI

17. Cotton denim yarnhaving an essentially dry and non-tackydiscontinuous coating covering the surface of said yarn offrom about 6to 8% by weight of a coagulated and set rubbery copolymer of from about55 to 70% byflweight of butadiene-1,3 and the balance acrylonitrile.18,. Cottondenim fabric having an essentially dry and non-tacky weftyarns and warp yarns, said warp yarns containing indigo and anessentially dry and non-tacky,

discontinuous coating covering the surface of said warp yarns of fromabout 6 to 8% by weight of a coagulated and set rubbery copolymenof fromabout 55 to 70% by weight of butadiene-1',3 and the balanceacrylonitrile, said warp yarns not being adhesively bound together.

References Cited in the file of this patent .UNITED STATES PATENTS1,399,230 Touchstone Dec. 6, 1921 1,902,833 Charch Mar. 28, 19332,016,813 Bulford Oct. 8, 1935 2,122,100 Kern June 28, 1938 2,132,901Iochum et al n--- Oct. 11, 1938 2,244,761 Brandwood June 10, 194]2,330,353 Henderson Sept. 28, 1943 2,368,948 Stallings Feb. 6, 19452,381,587 Griflin Aug.'7, 1945 2,447,538 Rust Aug. 24, 1948 2,483,236Berglund Sept. 20, 1949 2,489,943 Wilson Nov. 29, 1949 2,494,002 RumboldJan; 10, 1950 2,506,892 Radley May 9, 1950 2,589,919 Arundale Mar. 18,1952 2,628,151 Warmsley et al. Feb. 10, 1953 2,681,292 Ewing et al. June15, 1954 OTHER REFERENCES Gregory: Use and Applications of Chem. andRelated Materials, vol. II, 1944, page 169.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.2,840,442 June 24, 1958 Edward Abrams et a1.

It is hereby certified that error appears in the-printed specificationof the above numbered patent requiring correction and that the saidLetters Patent should read as corrected below.

Column 2, line 64, after "methyl" strike out the comma; column 4, line2, for -than" read then column 9 line 47', after "cracking"strike"out""the'"'first "the" and insert instead u of a; column 12,lines 31 and 32, SBIik$"ULI't "an essentially dry and non-=tacky"; line52, list of referencescited, under UNITED STATES PATENTS", for"2,483,236 Berglund" read 2,482,236 Berglund line 5'7 for "2,628,151Warmsley et'al." read 2 ,628 ,151 Walmsley et al.

Signed and sealed this 21st day of October 1958.

SEAL) ttest:

KARL H, AXLINE I ROBERT C. WATSON Commissioner of Patents AttestingOfl'icer

1. THE METHOD OF TREATING PREDOMINANTLY CELLULOSE CONTAINING YARN TOIMPROVE ITS ABRASION RESISTANCE, TO IMPROVE ITS RESISTANCE TO CROCKINGAND BLEEDING WHEN DYED AND TO REDUCE ITS SHED LOSS WHICH COMPRISESAPPLYING TO SAID YARN AN AQUEOUS DISPERSION CONTAINING FROM 3 TO 35% BYWEIGHT OF SOLIDS OF A RUBBERY MATERIAL SELECTED FROM THE GROUPCONSISTING OF A POLYMER OF A DIENE MONOMER AND A NITRILE MONOMER AND APOLYMER OF A DIENE MONOMER AND A NITRILE MONOMER WITH UP TO 35% BYWEIGHT OF SAID SECOND NAMED POLYMER OF A COPOLYMERIZED MONOMER SELECTEDFROM THE GROUP CONSISTING OF STYRENE, CHLOROSTYRENE METHACRYLIC ACID,METHYL ACRYLATE, METHYL METHACRYLATE, ETHYL ACRYLATE, ETHYLMETHACRYLATE, 2-VINYL PYRIDINE, METHYL VINYL KETONE AND VINYLIDENECHLORIDE, SAID DIENE BEING AN OPEN CHAIN CONJUGATED DIENE HYDROCARBONHAVING FROM 4 TO 8 CARBON ATOMS AND BEING PRESENT IN SAID POLYMERS IN ANAMOUNT OF FROM 3K TO 90% BY WEIGHT AND SAID NITRILE BEING SELECTED FROMTHE GROUP CONSISTING OF ACRYLONITRILE, METHYL ACRYLONITRILE, ETHYLACRYLONITRILE AND CHLOROACRYLONITRILE AND MIXTURES THEREOF, TO DEPOSITFROM ABOVE 2 TO 20% BY WEIGHT OF SAID SOLIDS ON SAID VARN AND DRYINGSAID YARN CONTAINING SAID SOLIDS TO A TOTAL MOISTURE CONTENT OF NOT MORETHAN ABOUT 5% BY WEIGHT TO COAGULATE, SET AND OBTAIN A DISCONTINUOUSCOATING OF SAID RUBBERY MATERIAL ON SAID YARN.